CN1136231C - Method for producing cellulose carbamate - Google Patents
Method for producing cellulose carbamate Download PDFInfo
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- CN1136231C CN1136231C CNB998109568A CN99810956A CN1136231C CN 1136231 C CN1136231 C CN 1136231C CN B998109568 A CNB998109568 A CN B998109568A CN 99810956 A CN99810956 A CN 99810956A CN 1136231 C CN1136231 C CN 1136231C
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- urea
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
- C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Disclosed is a method for producing cellulose carbamate by reacting cellulose with urea. The inventive method is characterized by a) activating or impregnating the cellulose by means of an optionally aqueous urea melt containing ammonia, b) by reacting the cellulose with the urea in an optionally aqueous urea melt at temperatures ranging from 100 DEG to 160 DEG C and by simultaneously removing the ammonia released during the reaction from the reaction mixture, using water as an entraining agent, and c) by separating, processing or purifying the raw product containing urea. The inventive method enables a homogeneous cellulose carbamate product with good technical utilization properties to be produced in a relatively simple manner without employing combustible organic solvents.
Description
The present invention relates to a kind of method of producing cellulose carbamate, this cellulose carbamate mainly can be used for producing cellulose carbamate or the cellulosic fiber of regenerated, yarn or film thus.The cellulose carbamate of producing according to described method can further be used as activated cellulose, for example is used for cellulosic esterification or etherification reaction.
Reacting the basis that forms cellulose carbamate by Mierocrystalline cellulose with urea is that urea (I) thermal destruction becomes isocyanic acid (II) and ammonia (III) (equation 1).Unsettled isocyanic acid is cellulosic intrinsic reactive component.Isocyanic acid and cellulosic alcohol radical (IV) react, and form carbamate groups, are expressed as cellulose carbamate (V) (equation 2).Equation 3 has been described the general reaction order.
Equation 1
Equation 2
Equation 3
Except isocyanic acid and fibrin reaction generate cellulose carbamate, because being urea with excessive existence, isocyanic acid reacts, can be observed undesirable biuret (VI) and formed (equation 4).
Equation 4
Knownly can produce the regenerated cellulose product, but this method is because processing step is complicated and used poisonous and inflammable chemical, so critical defect is arranged according to the xanthate method.This method is recorded in " Chemiefasern nach dem Viskoseverfahren, K.G tze, Springer-Verlag, 1967 ".Wherein especially disadvantageously used dithiocarbonic anhydride (CS
2Thereby) formed hydrogen sulfide (H
2S).
It is also known to Mierocrystalline cellulose and urea reaction are produced the Mierocrystalline cellulose that dissolves in the caustic soda dilute solution.EP-A-57105 has narrated a kind of method of producing cellulose carbamate, and it is based on Mierocrystalline cellulose and urea are dipped in the liquefied ammonia together.Ammonia serves as activator simultaneously, and it expands cellulosic crystalline structure, so that in described structure, have the urea of enough high densitys to exist, and wherein all Mierocrystalline cellulose hydroxyls demonstrate big to identical high reactivity with the hydroxyl that is present in the Mierocrystalline cellulose amorphous domain.After the ammonia evaporation, the cellulose conversion of in kiln this method being handled under the temperature on the fusing point of urea becomes cellulose carbamate.Reaction product water and washed with methanol are to isolate the excessive urea and the by product of formation.Its shortcoming is the liquefied ammonia mass consumption of (below 33 ℃) under the low temperature on the one hand.On the other hand, the very poor thermal conductivity of Mierocrystalline cellulose makes the Mierocrystalline cellulose inside of flooding with urea can not guarantee that controlled temperature is even.Next the ununiformity that the carbamate substituting group distributes on the cellulosic polymer chain causes product property inhomogeneous so that can not use on a large scale.
Method described in the EP-A 178 292 is characterized in that: Mierocrystalline cellulose floods with soda lye, then washes this soda lye with the water that contains urea and it is gone out, and then urea is imported into Mierocrystalline cellulose.Behind drying process subsequently, the Mierocrystalline cellulose heating a few hours of under the temperature of the fusing point that is higher than urea at least, in kiln, urea being flooded, water flushing then.The weak point of this method is to have used a large amount of soda lyes, and this solution can not wash out from Mierocrystalline cellulose fully.In addition, the sodium that contains in the wash-down water of crude product of a large amount of ureas and by product such as biuret only just can removed under the difficult condition very much.Process and be very difficult thereby also expend very much.All can be observed when in heating chamber, reacting in addition, for all above-mentioned shortcomings of EP-A 57 105.
Similar a kind of method can be known from German patent application DE-OS 196 35707.Cellulose suspension is extruded this suspension and is washed with alcohol in alkali lye or alkaline earth liquid.Wet Mierocrystalline cellulose then or with urea directly changes into cellulose carbamate, perhaps at first generates cellulose ester with acetic anhydride, and only after esterification, changes into cellulose carbamate with urea under 135 ℃ of-150 ℃ of temperature again.Its weak point also has been to use alkali lye or the alkaline earth liquid with above-mentioned shortcoming.The reaction of above-mentioned Mierocrystalline cellulose and diacetyl oxide makes because a further procedure of processing scale operation cellulose carbamate is complicated more, because need other purification phase to remove acetate.
Recommended Mierocrystalline cellulose and urea in dimethylbenzene, to react among the EP-A-97685.Here urea adds in dimethylbenzene/cellulosic inhomogeneous reaction mixture with particle form.Because urea is difficult to be dissolved in dimethylbenzene, so need very long and expensive reaction times.In addition, reaction obtains uneven product, is because because cellulosic crystal block section can not be approaching by reacting required urea, so mainly be that cellulosic pars amorpha and urea react.
German patent application DE-OS 4242437 has narrated urea and the reaction of Mierocrystalline cellulose in an organic reaction medium.For example toluene is as reaction medium.For with urea impregnation of fibers element, with Mierocrystalline cellulose 50 ℃ of aqueous solution with urea.After extruding excessive urea solution, change water section into the organic reaction medium, in reaction medium ebullient temperature following a few hours, change into cellulose carbamate with the Mierocrystalline cellulose of urea dipping by component distillation.After the filtration of crude product, reaction medium changes the aqueous solution of urea again into by component distillation.The gained cellulose carbamate is separated from urea solution and the water flushing by filtering.The weak point of this method is to have used burnable organic solvent as reaction medium on the one hand.In addition, water and reaction medium exchange twice mutually in this method, consume very high energy, and this must cause this facility investment very big very high with process cost.
In addition, corresponding method is to implement under the reaction conditions that impels biuret to form.Ammonia is insoluble basically when being higher than the boiling temperature of toluene for example, directly discharges from reaction chamber, that is: reaction product is shifted in chemical equilibrium.The amount that depends on used urea has a large amount of biuret productions when producing cellulose carbamate according to this method, it can not be processed with useful mode can not return reaction cycle.
Therefore the objective of the invention is to develop a kind of method of producing cellulose carbamate by Mierocrystalline cellulose and urea, this method has been avoided the above-mentioned shortcoming of prior art, in addition, also made even product, and used technical costs is lower and need not to use burnable organic solvent with good technique application performance.
According to the present invention, this purpose can reach like this,
A), by containing ammonia, optional aqueous urea melt activation or impregnation of fibers element,
B), in optional aqueous urea melt under 100 ℃ of-160 ℃ of temperature, Mierocrystalline cellulose reacts with urea, the ammonia water that discharges in the reaction process from reaction mixture, remove simultaneously as entrainment agent and
C), isolate contain the urea crude product and processing or purifying.
Be enough to surprisingly, found to activate simultaneously with impregnation of fibers with containing the semicarbazide melt that plain and cellulosic reaction is also available to be easy to finish and without organic solvent.In addition, the method according to this invention obtains having the product of the uniform substituent distribution of good solubility and filterableness, and this point is not seen before.
The method according to this invention comprises at least three steps.The first step a) in, Mierocrystalline cellulose is activated simultaneously dipping under 80 ℃ of-160 ℃ of temperature.As everyone knows, different sources is 40-70% with different pretreated cellulose crystallities, compares with the pars amorpha, and the diffusion of solvent and reactant reduces greatly in the crystalline region.This makes cellulosic reaction can cause product inhomogeneous usually.This be since the pars amorpha than crystalline region and can not arrive regional level of response height.Therefore, the reactivity of pars amorpha and crystalline region is complementary just can obtains uniform reaction product, this point can be realized by so-called activation.Therefore activation is a particularly important, because crystalline region and pars amorpha are evenly distributed and substituting group is evenly distributed on polymer chain has represented the cellulose carbamate application, for example as the basic mass parameter of fiber raw material.
Must will regard an essential characteristic of the present invention as with containing semicarbazide melt activated cellulose in the step a), not moisture or aqueous here urea melt is all suitable equally.The water-content of urea melt can be from the 0-15% changes in weight, and preferred 0.5-5% weight is benchmark with the amount of used urea.Because reaction has formed the ammonia that is enough to the activated cellulose crystalline region described in the equation (1) in the urea melt, its concentration depends on ground pressure and temperature.When the ammonia concentration that exists in the urea melt was enough to be used for activating, the ammonia or the ammoniacal liquor that add other gas form in the urea melt can be abandoned in the method for the invention.For example situation is, the urea melt that is used for activated cellulose maintained the temperature at more than 133 ℃ several minutes to several hours.According to an embodiment preferred, about 140 ℃ with Flashmelt equipment with the urea fusion and pump into the reactor that temperature remains on 140 ℃.But urea also can solid matter, for example with crystal, spherical or granular, directly adds reactor and fusion therein.In addition, urea also can add in the reactor by concentrated aqueous solutions.Temperature of reactor preferably remains on about 100 ℃ in this case.
Mierocrystalline cellulose imports with wet or drying regime and contains in urea, ammonia and the optional aqueous urea melt to take off fibrillation form or sheet-like fiber prime form.According to an embodiment preferred, do or wet Mierocrystalline cellulose directly import through a metering approach may aqueous urea melt and by kneading or stirring with the urea complete wetting or impregnated in the moisture melt.Mierocrystalline cellulose preferred degree of polymerization (DP) is 120-2,000, and particularly 200-600 preferably at 25 ℃-160 ℃, particularly imports in the urea melt under the temperature about 135 ℃.According to the present invention, activation or the dipping of Mierocrystalline cellulose in the urea melt generally continues 10 minutes-about 5 hours.
At 100 ℃-160 ℃, under preferred 130 ℃-150 ℃, become cellulose carbamate in the step b) cellulose conversion.
Because step b) also can be finished the method according to this invention, step a) and b in optional aqueous urea melt) can be combined in single still reaction.The urea melt not only serves as cellulosic reactant, simultaneously also is used for the bad thermal conduction of compensation fibre element as heat exchange agent.According to an embodiment preferred, step a) and b) in use urea, particularly 10-25 that 3-50 doubly measures doubly, be benchmark with the Mierocrystalline cellulose dry weight.Think particularly preferably to be excessive 15 times urea, a large amount of relatively ureas possesses the heat transfer characteristic of having narrated.In addition, the Mierocrystalline cellulose of ratio has good stirring capacity and pumping power shown in the urea melt.
Must be with reactions steps b) in the ammonia of emitting use water as entrainment agent and from reaction mixture, remove and regard essential characteristic of the present invention as.Become cellulose carbamate for Mierocrystalline cellulose with the urea successive reaction, removing deammoniation from reaction mixture is a basic premise.According to an embodiment preferred,,, remove the ammonia that contains in reaction chamber and the reaction mixture to distillate the entrainment agent of water as ammonia by continuous measurement supplied water in reaction mixture.This variation of this method is very wonderful for a people with ordinary skill, is an obstacle because with regard to the existence of knowledge situation water of today Mierocrystalline cellulose and urea are reacted into cellulose carbamate.The amount of amount entry depends on equilibrium temperature final in the reactor.The amount of preferred amounts entry makes the evaporation enthalpy of institute's supplied water make temperature of reaction reduce by 1 ℃-20 ℃, particularly 5 ℃-10 ℃.The nitrogen that depends on the carbamate of required replacement degree or introducing, the reactions steps b of the inventive method) required time is that several minutes arrives several hours.Preferred 0.5-6 of reaction times hour, particularly 1.0-1.5 hour.
This method can be for example implemented in stirring tank continuously according to the present invention, also can be for example mediate reactor (as: Discotherm B.Conti of the company List, SwitzeHand) in discontinuous carrying out.
Reactions steps b) preferably interrupt by adding water, the supply of water for example is metered into reactor by pump.In step c), isolate afterwards and contain the urea crude product and process or purifying.
In continuous processing (kneading reactor), the reaction mass of viscosity preferably separates by screw rod or pump, and reaction mass is as being sent to rinse step (as: pulsating whizzer).Subsequently, purifying crude product, preferred water flushing.This for example can finish crude product by a rinsing area, the rinsing area crude product for example on a band filter adverse current contact with fresh water and remove remaining urea and by product.The cellulose carbamate of gained can directly further be processed or further be processed through a drying program of following then according to the present invention.
The special favourable part of the inventive method is to transform required energy and imports reactive system by the urea melt.The big thermal capacitance of urea makes might control definite temperature, and this scale operation to even product is basic prerequisite.Known relatively method is finished the heat input by air (loft drier) or through the organic reaction medium, and this is basic favourable part.
The inventive method additional advantage is that urea is nontoxic and not flammable.The ammonia of gained can be received and further form ammoniacal liquor at rinse-system at an easy rate by gas phase.Excessive urea can reclaim or utilization more by this way through evaporation from wash-down water.
In addition, owing to method of the present invention is used lower technical costs and with an organic solvent do not obtained even product, it is very suitable for cellulose carbamate with scale operation.
The following examples will be explained the present invention in more detail.
Embodiment 1:
The 200g urea is added in the stirring tank at 150 ℃ with melt.This melt under agitation remained on this temperature 15 minutes.This is added 30gDP is not activated cellulose of 350 drying.This reaction mixture stirred 90 minutes at 150 ℃, was metered into through dropping funnel during this period and amounted to 100ml water.Water and ammonia are constantly removed from reaction mixture through the distillation bridge in the reaction process.After 90 minutes, add temperature and remain on 80 ℃ water and make cellulose suspension in water, and make it in reactor, to keep again 5 minutes, stir simultaneously.Crude product leaches subsequently, and washes repeatedly with a small amount of hot water, amounts to 31.After 40 ℃ of dryings, obtain nitrogen content and be 2.20% and DP be 320 product, be 8.5% weight at-5 ℃ of these products meltage in 10% soda lye.
Embodiment 2 (contrast):
Method is with embodiment 1, but need not metered supply water in the reaction process and remove deammoniation.Obtain nitrogen content 0.65%, DP is 324 cellulose carbamate.-5 ℃ of following products are insoluble to 10% soda lye.
Embodiment 3:
The 100g urea is added in the laboratory malaxator of opening at 150 ℃ with melt.Melt was placed 60 minutes in malaxator at 150 ℃.Adding 100gDP to described melt then is 350 wet fiber element (water content of 50% weight).Under the condition that evaporation is anhydrated melt is cooled to about 100 ℃.After evaporation was anhydrated, the temperature of reaction mixture rose to 150 ℃ again.When reaching 150 ℃ temperature, be metered into water and make that temperature-stable remains on 145 ℃ in the malaxator.React after 90 minutes, process as embodiment 1 and 2.Obtain nitrogen content 3.05%, DP is 318 cellulose carbamate, dissolves in 10% soda lye in the time of-5 ℃ and can reach 9.0% weight.
Claims (18)
1. method of producing cellulose carbamate by the reaction of Mierocrystalline cellulose and urea is characterized in that:
A), by containing ammonia, moisture or water-free urea melt is at 80-160 ℃ of activation or impregnation of fibers element down, the treatment time is 10 minutes to 5 hours,
B), in moisture or water-free urea melt under 100 ℃ of-160 ℃ of temperature, Mierocrystalline cellulose and urea reaction 0.5-6.0 hour, the ammonia water that discharges in the reaction process from reaction mixture, remove simultaneously as entrainment agent and
C), isolate contain the urea crude product and processing or purifying.
2. the method for claim 1 is characterized in that the cellulosic degree of polymerization that uses is 120-2,000.
3. the method for claim 1 is characterized in that the cellulosic degree of polymerization that uses is 200-600.
4. each method of claim 1-3 is characterized in that step a) and b) in the amount of used urea, be benchmark with the Mierocrystalline cellulose dry weight, be 3-50 doubly.
5. the method for claim 4 is characterized by step a) and b) in the amount of used urea, be benchmark with the Mierocrystalline cellulose dry weight, be 10-25 doubly.
6. each method of claim 1-4 is characterized in that step a) and b) in the water-content of urea melt be 0-15% weight, be benchmark with used urea amount.
7. the method for claim 6 is characterized in that step a) and b) in the water-content of urea melt be 0.5-5.0% weight, be benchmark with used urea amount.
8. each method of claim 1-7 is characterized in that step a) and b) carry out with single still reaction.
9. each method of claim 1-8 is characterized in that the temperature of reaction in the step b) is set in 130 ℃-150 ℃.
10. each method of claim 1-9 is characterized in that the step b) time of carrying out is 1.0-1.5 hour.
11. each method of claim 1-10 is characterized in that the ammonia that generates in the step b) adds by continuous measurement and steams water and remove from reaction mixture.
12. the method for claim 11 is characterized in that the water management of temperature of reaction by metered supply.
13. the method for claim 11 is characterized in that measuring the evaporation of water enthalpy temperature of reaction is reduced by 1 ℃-20 ℃.
14. the method for claim 13 is characterized in that measuring the evaporation of water enthalpy temperature of reaction is reduced by 5 ℃-10 ℃.
15. each method of claim 1-14 is characterized in that being reflected at discontinuous carrying out in the stirring tank.
16. each method of claim 1-14 is characterized in that being reflected at one and mediates in the reactor and carry out continuously.
17. each method of claim 1-16 is characterized in that step b) interrupts by adding water.
18. each method of claim 1-17 is characterized in that crude product water flushing purifying in step c).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19835688.9 | 1998-08-07 | ||
| DE19835688A DE19835688A1 (en) | 1998-08-07 | 1998-08-07 | Process for the production of cellulose carbamate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1318072A CN1318072A (en) | 2001-10-17 |
| CN1136231C true CN1136231C (en) | 2004-01-28 |
Family
ID=7876753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998109568A Expired - Fee Related CN1136231C (en) | 1998-08-07 | 1999-07-30 | Method for producing cellulose carbamate |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1100831B1 (en) |
| KR (1) | KR100405799B1 (en) |
| CN (1) | CN1136231C (en) |
| AT (1) | ATE226597T1 (en) |
| DE (2) | DE19835688A1 (en) |
| ES (1) | ES2183596T3 (en) |
| WO (1) | WO2000008060A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544745A (en) * | 2015-09-17 | 2017-03-29 | 宜宾丝丽雅集团有限公司 | Production method of cellulose carbamate fiber filament |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10023753A1 (en) * | 2000-05-15 | 2001-11-29 | Zimmer Ag | Method and device for treating pulp with urea and ammonia |
| KR100364508B1 (en) * | 2000-09-21 | 2002-12-12 | (주)이앤텍 | Bio-polymer amine and manufact uring method of same |
| DE10162791C1 (en) * | 2001-12-20 | 2002-12-19 | Fraunhofer Ges Forschung | Preparation of cellulose carbamate by reaction of cellulose with urea in the presence of molten or dissolved urea with the aid of electromagnetic radiation useful for the production of fibers, films, beads, and sponges |
| WO2003064476A1 (en) * | 2002-01-29 | 2003-08-07 | Valtion Teknillinen Tutkimuskeskus | Method for manufacturing cellulose carbamate |
| DE10223174A1 (en) * | 2002-05-24 | 2003-12-11 | Fraunhofer Ges Forschung | Process for the production of cellulose carbamate moldings |
| DE10223172B4 (en) * | 2002-05-24 | 2004-05-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the production of cellulose carbamate by means of reactive extrusion and the use of the process products for the production of moldings |
| DE10223171A1 (en) * | 2002-05-24 | 2003-12-11 | Zimmer Ag | Process for the production of cellulose carbamate |
| CN100427508C (en) * | 2005-10-27 | 2008-10-22 | 东华大学 | Method for preparing cellulose carbamate utilizing supercritical carbon dioxide |
| DE102011118928B4 (en) | 2011-11-21 | 2017-12-07 | Bourns, Inc. | Rotation angle sensor |
| EP3728332A1 (en) * | 2017-12-21 | 2020-10-28 | FRAUNHOFER-GESELLSCHAFT zur Förderung der angewandten Forschung e.V. | Method for producing cellulose carbamate, cellulose carbamate and also mouldings produced therefrom |
| FI129441B (en) * | 2019-11-20 | 2022-02-28 | Andritz Oy | Method for producing cellulose carbamate |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI62318C (en) * | 1981-01-27 | 1982-12-10 | Neste Oy | FORM OF CELLULOSE DERIVATIVES OF FRAMSTAELLNING AV ETT ALKALILOESLIGT |
| FI64602C (en) * | 1981-12-30 | 1983-12-12 | Neste Oy | FORM OF CELLULOSE DERIVATIVES |
| FI67561C (en) * | 1982-12-08 | 1985-04-10 | Neste Oy | FOERFARANDE FOER UPPLOESNING AV CELLULOSAKARBAMAT |
| FI66624C (en) * | 1983-11-02 | 1984-11-12 | Neste Oy | FOERFARANDE FOER FRAMSTAELLNING AV CELLULOSAKARBAMATFIBRER ELLER -FILMER |
| FI67562C (en) * | 1984-03-12 | 1985-04-10 | Neste Oy | FOERFARANDE FOER FRAMSTAELLNING AV CELLULOSAKARBAMAT |
| US5378827A (en) * | 1992-12-16 | 1995-01-03 | Zimmer Aktiengesellschaft | Process for the production of cellulose carbamate |
| PL310288A1 (en) * | 1995-09-04 | 1997-03-17 | Inst Wlokien Chem | Method of obtaining cellulose carbamate |
| DE19628277C2 (en) * | 1996-07-12 | 1998-07-09 | Rhodia Ag Rhone Poulenc | Process for activating a cellulose and urea-containing mixture, activated cellulose and urea-containing mixture and use of the activated mixture for the production of cellulose carbamate |
-
1998
- 1998-08-07 DE DE19835688A patent/DE19835688A1/en not_active Withdrawn
-
1999
- 1999-07-30 WO PCT/EP1999/005462 patent/WO2000008060A1/en active IP Right Grant
- 1999-07-30 ES ES99939417T patent/ES2183596T3/en not_active Expired - Lifetime
- 1999-07-30 DE DE59903189T patent/DE59903189D1/en not_active Expired - Lifetime
- 1999-07-30 EP EP99939417A patent/EP1100831B1/en not_active Expired - Lifetime
- 1999-07-30 KR KR10-2001-7001665A patent/KR100405799B1/en not_active IP Right Cessation
- 1999-07-30 AT AT99939417T patent/ATE226597T1/en not_active IP Right Cessation
- 1999-07-30 CN CNB998109568A patent/CN1136231C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544745A (en) * | 2015-09-17 | 2017-03-29 | 宜宾丝丽雅集团有限公司 | Production method of cellulose carbamate fiber filament |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2183596T3 (en) | 2003-03-16 |
| DE59903189D1 (en) | 2002-11-28 |
| ATE226597T1 (en) | 2002-11-15 |
| EP1100831A1 (en) | 2001-05-23 |
| WO2000008060A1 (en) | 2000-02-17 |
| DE19835688A1 (en) | 2000-02-10 |
| KR20010072335A (en) | 2001-07-31 |
| CN1318072A (en) | 2001-10-17 |
| EP1100831B1 (en) | 2002-10-23 |
| KR100405799B1 (en) | 2003-11-14 |
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